US5556618A - Antibacterial electret material - Google Patents
Antibacterial electret material Download PDFInfo
- Publication number
- US5556618A US5556618A US08/108,644 US10864493A US5556618A US 5556618 A US5556618 A US 5556618A US 10864493 A US10864493 A US 10864493A US 5556618 A US5556618 A US 5556618A
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- US
- United States
- Prior art keywords
- antibacterial
- ion
- compound
- electret
- metal
- Prior art date
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 37
- -1 amine compound Chemical class 0.000 claims abstract description 76
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 45
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 229920005613 synthetic organic polymer Polymers 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 7
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 7
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 26
- 239000004743 Polypropylene Substances 0.000 description 24
- 229920001155 polypropylene Polymers 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 239000004744 fabric Substances 0.000 description 17
- 239000004750 melt-blown nonwoven Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 8
- KHSJSHLTDJITNE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methoxy-ethylphosphinic acid Chemical compound CCP(O)(=O)OCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KHSJSHLTDJITNE-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 229910015133 B2 O3 Inorganic materials 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 229910004742 Na2 O Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/021—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric
- H01G7/023—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric of macromolecular compounds
Definitions
- the present invention relates to a material having both an antibacterial activity and an electret property and useable in the fields of filters, food packaging, medical materials, working clothes, and so forth.
- Japanese patent application Kokai publication No. 3-186309 discloses an air filter comprising an antibacterial nonwoven fabric composed of a fiber and, added thereto, an inorganic antibacterial zeolite and an electret nonwoven fabric laminated on the antibacterial nonwoven fabric.
- this air filter could suppress the propagation of trapped bacteria on the side of the antibacterial nonwoven fabric, it was disadvantageous in that, on the side of the electret nonwoven fabric, trapped bacteria propagated and emitted an offensive odor or rescattered to contaminate the atmosphere of a room. Further, since the electret property was not imparted to the air filter as a whole, the performance of the filter lowered.
- Japanese patent application Kokai publication No. 62-42715 discloses a composite material comprising an electret nonwoven material and, superimposed thereon, a nonwoven fabric subjected to an antibacterial treatment. This composite material, however, had a similar drawback.
- An object of the present invention is to provide an antibacterial electret material having a good charge stability and an electret property while maintaining an antibacterial activity.
- the antibacterial electret material comprising the above-described synthetic organic polymer contains 0.01 to 2% by weight of an electret stabilizer and 0.1 to 4% by weight of a metal-ion-containing inorganic compound as an antibacterial agent.
- phenol compound examples include 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
- Q is a surface charge density, (coulomb/cm 2 ).
- the antibacterial activity is measured by the shake flask method. Specifically, a sample was thrown into a, suspension of a test bacterium (Staphylococcus aureus) and the suspension was shaken in a hermetically sealed container at a rate of 150 times/min for 1 hour. Thereafter the number of vial cells was counted to determine the percentage reduction of the cells based on the initial number of cells.
- a test bacterium Staphylococcus aureus
- a melt-blown nonwoven fabric having a weight per unit area of 100 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- 0.2% by weight of a calcium salt of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a hindered phenol compound) and 0.2% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) were incorporated as the electret stabilizers into the polypropylene and 0.8% by weight of a zeolite carrying a silver ion was incorporated as the antibacterial agent into the polypropylene.
- a voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret propertly thereto.
- the above-described polypropylene was used to produce a conventional melt-blown nonwoven fabric containing neither an electret stabilizer nor and antibacterial agent, and the antibacterial activity was measured. As a result, the percentage reduction was found to be 3%.
- the conventional melt-blown nonwoven fabric brought about occurrence of an offensive odor.
- a spunbonded nonwoven fabric was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- a voltage of 25 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- the electret nonwoven fabric had a surface charge density of 5 ⁇ 10 31 10 C/cm 2 , and the two surfaces had respectively positive and negative polarities.
- the antibacterial activity as measured by the shake flask method was 65% in terms of the percentage reduction.
- This electret nonwoven fabric was used as a packaging material for oranges. As a result, it did not bring about generation of fungi for 3 months. On the other hand, occurrence of fungi was observed in one month for the conventional spunbonded nonwoven fabric.
- the above-described polypropylene was used to produce a melt-blown nonwoven fabric containing neither an electret stabilizer nor an antibacterial agent, and the antibacterial activity was measured. As a result, the percentage reduction was found to be 4%.
- a melt-blown nonwoven fabric comprising a polypropylene having a weight per unit area of 100 g/m 2 was produced in the same manner as that of Example 1, except that no antibacterial agent was incorporated. Specifically, in the melt-blown nonwoven fabric, 0.2% by weight of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a metallic salt hindered phenol) and 0.1% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) were incorporated as the electret stabilizers. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate a metallic salt hindered phenol
- the electret nonwoven fabric had a surface charge density of 8.5 ⁇ 10 -10 C/cm 2 .
- the antibacterial activity as measured by the shake flask method was 4% in terms of the percentage reduction so that the antibacterial activity was unsatisfactory.
- a melt-blown nonwoven fabric having a weight per unit area of 100 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm. 0.5% by weight of 2,4,4-trichloro-2'-hydroxydiphenyl ether (an antibacterial agent described in Japanese patent application Kokai publication No. 62-42716), together with an acrylic resin as an anchoring agent, was deposited as an electret stabilizer on the melt-blown nonwoven fabric. A voltage of 25 kv was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- the electret nonwoven fabric had a surface charge density of 0.2 ⁇ 10 -10 C/cm 2 , that is, the electret property was hardly imparted.
- a melt-blown nonwoven fabric having a weight per unit area of 100 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- 0.15% by weight of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid (a nitrogenous hindered phenol compound) as the electret stabilizer and 1% by weight of a zeolite carrying a silver ion as the anchoring antibacterial agent were incorporated into the polypropylene.
- a voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- a melt-blown nonwoven fabric having a weight per unit area of 100 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- 0.2% by weight of distearyl pentaerythritol diphosphite (a phosphorus compound) as the electret stabilizer and 1.2% by weight of a water-soluble glass carrying a silver ion as the antibacterial agent were incorporated into the polypropylene.
- a voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- the surface charge density and antibacterial activity as measured by the shake flask method were 7 ⁇ 10 -10 C/cm 2 and 67% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
- a melt-blown nonwoven fabric having a weight per unit area of 10 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- a voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- the surface charge density and antibacterial activity as measured by the shake flask method were 4 ⁇ 10 -10 C/cm 2 and 69% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
- a melt-blown nonwoven fabric having a weight per unit area of 100 g/m 2 was produced from a polypropylene having a volume resistivity of 10 ⁇ 10 16 ⁇ cm.
- 0.2% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) as the antibacterial agent and 1% by weight of zirconium phosphate carrying a silver ion as the antibacterial agent were incorporated into the polypropylene.
- a voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto.
- the surface charge density and antibacterial activity as measured by the shake flask method were 4 ⁇ 10 -10 C/cm 2 and 70% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
- the metal ion contained, in the antibacterial agent inhibits the growth of bacteria and microbial cells to exhibit an antibacterial effect and, at the same time, the electret stabilizer traps electric charges to exhibit an electret effect.
- the electret material of the present invention has a combination of an antibacterial activity with an electret property. Further, these charges remain stable even when environmental conditions, humidity and temperature vary, which renders the electret material of the present invention useable in making filters, packaging materials, agricultural materials, wipers, various covering materials, head-gear, medical materials, masks, and so forth.
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Filtering Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
An antibacterial electret material which consists of a synthesized organic polymer having a volume resistivity of not less than 1013 Ω·cm and containing 0.01 to 2% by weight of one kind of electret stabilizer selected from the group composed of a hindered amine compound, a nitrogen-containing hindered phenol compound, a metallic salt hindered phenol compound, a phenol compound, a sulfur compound and a phosphorus compound and 0.1 to 4% by weight of metal ion-containing inorganic compound, and which has a surface density of charge of not less than 1×10-10 coulomb/cm2.
Description
The present invention relates to a material having both an antibacterial activity and an electret property and useable in the fields of filters, food packaging, medical materials, working clothes, and so forth.
Japanese patent application Kokai publication No. 62-42716 discloses as an antibacterial electret material a filter material formed by subjecting the surface of a fiber to an antibacterial treatment with an antibacterial agent and further subjecting the treated fiber to a treatment for imparting an electret property. In this filter material, however, the volume resistivity of the surface of the fiber was reduced because the antibacterial treatment was conducted by using an organic antibacterial agent and a surfactant for dispersing the antibacterial agent. For this reason, the filter material had a problem that, even after the treatment for imparting an electret property, the quantity of electric charge was small and the charge decayed rapidly.
Japanese patent application Kokai publication No. 3-186309 discloses an air filter comprising an antibacterial nonwoven fabric composed of a fiber and, added thereto, an inorganic antibacterial zeolite and an electret nonwoven fabric laminated on the antibacterial nonwoven fabric. Although this air filter could suppress the propagation of trapped bacteria on the side of the antibacterial nonwoven fabric, it was disadvantageous in that, on the side of the electret nonwoven fabric, trapped bacteria propagated and emitted an offensive odor or rescattered to contaminate the atmosphere of a room. Further, since the electret property was not imparted to the air filter as a whole, the performance of the filter lowered.
Japanese patent application Kokai publication No. 62-42715 discloses a composite material comprising an electret nonwoven material and, superimposed thereon, a nonwoven fabric subjected to an antibacterial treatment. This composite material, however, had a similar drawback.
Studies conducted by the present inventors revealed that the process wherein the formed nonwoven fabric was subjected first to an antibacterial treatment and then to a treatment for imparting an electret property had a fundamental problem that it was difficult to impart a good electret property and, further, since the process time was lengthened, the product cost was increased.
On the other hand, the process wherein the formed nonwoven fabric was subjected first to a treatment for imparting an electret property and then to an antibacterial treatment had a drawback that the antibacterial treatment deteriorated the electret performance and a problem that the process time was similarly lengthened and hence the product cost was increased.
An object of the present invention is to provide an antibacterial electret material having a good charge stability and an electret property while maintaining an antibacterial activity.
The antibacterial electret material of the present invention which can attain the above-described object is characterized by having a surface charge density of 1×10-10 C/cm2 or above and comprising a synthetic organic polymer having a volume resistivity of 1013 Ω·cm or above and containing 0.01 to 2% by weight of at least one electret stabilizer selected from the group consisting of a hindered amine compound, a nitrogenous hindered phenol compound, a metallic salt hindered phenol compound, a phenol compound, a sulfur compound and a phosphorus compound and 0.1 to 4% by weight of a metal-ion-containing inorganic compound.
FIG. 1 is a schematic diagram showing a method of measuring the surface charge density.
In the present invention, examples of the synthetic organic polymer having a volume resistivity of 1013 Ω· cm or above include polyolefins, polyesters, fluororesins, acrylic resins and polyamide resins, among which polyolefin polymers, such as polyethylene and polypropylene, are preferred.
The antibacterial electret material comprising the above-described synthetic organic polymer contains 0.01 to 2% by weight of an electret stabilizer and 0.1 to 4% by weight of a metal-ion-containing inorganic compound as an antibacterial agent.
In the present invention, all the contents are expressed in % by weight.
The electret stabilizer is preferably at least one compound selected from the group consisting of a hindered amine compound, a nitrogenous hindered phenol compound, a metallic salt hindered phenol compound, a phenol compound, a sulfur compound and a phosphorus compound.
Examples of the hindered amine compound include poly[{(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4- diyl}(2,2,6,6-tetramethyl-4-piperidyl)-imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate.
Examples of the nitrogenous hindered phenol compound include 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid.
Examples of the metallic salt hindered phenol compound include a calcium salt of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate, a nickel salt of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate and a magnesium salt of these compounds.
Examples of the phenol compound include 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
Examples of the sulfur compound include distearyl thiodipropionate and dilauryl thiodipropionate.
Examples of the phosphorus compound include distearyl pentaerythritol diphosphite.
Although the effect of the present invention can be attained when each of the electret stabilizers is contained alone in the synthetic organic polymer, a better effect can be attained when the electret stabilizers are used in combination of two or more of them. Although the reason has not been elucidated yet, it is conceivable to reside in that the individual electret stabilizers are different form each other in the charge holding mechanism and a combination of different charge holding mechanisms contributes to an increase in the effect of stabilizing the electret.
In the present invention, examples of the metal-ion-containing inorganic compound as the antibacterial agent include metal-ion-containing zeolite, soluble glass, zirconium phosphate, titanium phosphate and tin phosphate, among which metal-ion-containing zeolite, soluble glass and zirconium phosphate are particularly preferred.
Examples of the metal ion of the metal-ion-containing inorganic compound include silver, copper, zinc, mercury, tin, lead, bismuth, chromium and thallium ions, among which silver ion is particularly useful, and the silver ion may be in the form of a complex ion comprising the silver ion and other metal ion. Further, a combination of various antibacterial agents is also,effective.
The soluble glass comprises B2 O3, SiO2, Na2 O or the like and when silver ion is to be carried thereon Ag2 O is preferred therefor.
The synthetic organic polymer material containing the electret stabilizer and the metal-ion-containing inorganic compound (hereinafter referred to as the "antibacterial agent") is formed into a fiber, film, woven fabric, nonwoven fabric, paper or knit. The conventional forming means, such as yarn making, texturing, papermaking or film formation, may be applied therefor.
The electret stabilizer and the antibacterial agent can be incorporated into the synthetic organic polymer by a method called "incorporation". For example, the incorporation can be conducted by mixing them into the synthetic organic polymer in the form of a chip or feeding them into an extruder.
The formed fiber, woven fabric, knit, nonwoven fabric paper film or other material is then subjected to the conventional treatment for imparting an electret property, for example, a treatment for imparting an electret property under a high d.c. voltage to provide an electret material having a high charge density, i.e., usually having a surface charge density of 1×10-10 C/cm2 or above.
According to the finding of the present inventors, when the material is subjected to the treatment for imparting an electret property in the form of a sheet, such as a woven fabric, nonwoven fabric, paper or film, the resultant electret material has a surface charge density of 2×10-10 to 1×10-8 C/cm2. Further in the sheet, the electric polarity of one surface thereof is different from that of the other surface.
The contents of the electret stabilizer and the antibacterial agent are important for attaining an electret property while maintaining an antibacterial activity. The content of the electret stabilizer should be 0.01% by weight or more from the viewpoint of the stability of the electret. However, if the content is excessively high, the effect lowers, so that the upper limit of the electret stabilizer is preferably 2% by weight.
The content of the antibacterial agent should be 0.1% by weight or more from the viewpoint of the antibacterial activity. For the antibacterial agent as well, if the content is excessively high, the electret property is deteriorated, so that the upper limit of the content is preferably 4% by weight.
The antibacterial electret material of the present invention is constructed so that the weight per unit area is preferably 10 to 200 g/m2, still preferably 20 to 100 g/m2. That is, it is relatively light. Such a light weight cannot be attained when a material having an antibacterial activity and a material having an electret property are separately prepared and then combined with each other, because the total weight becomes large. By contrast, the antibacterial electret material of the present invention is light while maintaining both the properties, which renders it significant.
In the present invention, the surface charge density of the electret is measured by the method illustrated in FIG. 1. In the figure, an electret sample 3 is sandwiched between electrodes 1 and 2 and an induced charge is stored in a known capacitor 4. The potential is measured with an electrometer 5 and the surface charge density is determined according to the following equation:
surface charge density Q=C×V
wherein C is a capacity of a known capacitor (farad),
V is a voltage (volt), and
Q is a surface charge density, (coulomb/cm2).
Further, in the present invention, the antibacterial activity is measured by the shake flask method. Specifically, a sample was thrown into a, suspension of a test bacterium (Staphylococcus aureus) and the suspension was shaken in a hermetically sealed container at a rate of 150 times/min for 1 hour. Thereafter the number of vial cells was counted to determine the percentage reduction of the cells based on the initial number of cells.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the fabric, 0.2% by weight of a calcium salt of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a hindered phenol compound) and 0.2% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) were incorporated as the electret stabilizers into the polypropylene and 0.8% by weight of a zeolite carrying a silver ion was incorporated as the antibacterial agent into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret propertly thereto.
The electret nonwoven fabric had a surface charge density of 8×10-10 C/cm2, and the two surfaces had respectively positive and negative polarities. The antibacterial activity was measured by the shake flask method. As a result, the percentage reduction was found to be 75%.
For comparison, the above-described polypropylene was used to produce a conventional melt-blown nonwoven fabric containing neither an electret stabilizer nor and antibacterial agent, and the antibacterial activity was measured. As a result, the percentage reduction was found to be 3%.
When the electret nonwoven fabric provided in Example 1 was used as a filter, the efficiency of trapping bacteria was 95%. Even after the use of the filter within a building for half a year, the filter brought about neither generation of bacteria nor occurrence of an offensive odor.
On the other hand, the conventional melt-blown nonwoven fabric brought about occurrence of an offensive odor.
A spunbonded nonwoven fabric was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of this fabric, 0.1% by weight of poly[{(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino)}] (a hindered amine compound) and 0.1% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) were incorporated as the electret stabilizers into the polypropylene, and 1% by weight of a water-soluble glass carrying a silver ion was incorporated as the antibacterial agent into the polypropylene.
A voltage of 25 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The electret nonwoven fabric had a surface charge density of 5×1031 10 C/cm2, and the two surfaces had respectively positive and negative polarities. The antibacterial activity as measured by the shake flask method was 65% in terms of the percentage reduction.
This electret nonwoven fabric was used as a packaging material for oranges. As a result, it did not bring about generation of fungi for 3 months. On the other hand, occurrence of fungi was observed in one month for the conventional spunbonded nonwoven fabric.
A melt-blown nonwoven fabric having a weight per unit area of 50 g/m2 was produced by using a raw material comprising a polypropylene having a volume resistivity of 10×1016 Ω·cm and, incorporated therein as the stabilizers, 0.1% by weight of a calcium salt of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a hindered phenol compound) and 0.1% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) and, further incorporated therein as the antibacterial agent, 1.1% by weight of zirconium phosphate carrying a silver ion.
A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The electret nonwoven fabric had a surface charge density of 9×10-10 C/cm2, and the two surfaces had respectively positive and negative polarities. The antibacterial activity as measured by the shake flask method was 72% in terms of the percentage reduction.
For comparison, the above-described polypropylene was used to produce a melt-blown nonwoven fabric containing neither an electret stabilizer nor an antibacterial agent, and the antibacterial activity was measured. As a result, the percentage reduction was found to be 4%.
A melt-blown nonwoven fabric comprising a polypropylene having a weight per unit area of 100 g/m2 was produced in the same manner as that of Example 1, except that no antibacterial agent was incorporated. Specifically, in the melt-blown nonwoven fabric, 0.2% by weight of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a metallic salt hindered phenol) and 0.1% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) were incorporated as the electret stabilizers. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The electret nonwoven fabric had a surface charge density of 8.5×10-10 C/cm2. However, the antibacterial activity as measured by the shake flask method was 4% in terms of the percentage reduction so that the antibacterial activity was unsatisfactory.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. 0.5% by weight of 2,4,4-trichloro-2'-hydroxydiphenyl ether (an antibacterial agent described in Japanese patent application Kokai publication No. 62-42716), together with an acrylic resin as an anchoring agent, was deposited as an electret stabilizer on the melt-blown nonwoven fabric. A voltage of 25 kv was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The electret nonwoven fabric had a surface charge density of 0.2×10-10 C/cm2, that is, the electret property was hardly imparted.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.15% by weight of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid (a nitrogenous hindered phenol compound) as the electret stabilizer and 1% by weight of a zeolite carrying a silver ion as the anchoring antibacterial agent were incorporated into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity of the electret nonwoven fabric were measured by the above-described methods. As a result, it was found that the surface charge density and the antibacterial activity as measured by the shake flask method were 5×10-10 C/cm2 and 70%, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties. EXAMPLE 5
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.4% by weight of distearyl thiodipropionate (a sulfur compound) as the electret stabilizer and 0.6% by weight of a zeolite carrying a silver ion as an antibacterial agent were incorporated into the polypropylene. A voltage of 30 kv was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity as measured by the shake flask method were 6×10-10 C/cm2 and 68% in terms of the percentage seduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.2% by weight of distearyl pentaerythritol diphosphite (a phosphorus compound) as the electret stabilizer and 1.2% by weight of a water-soluble glass carrying a silver ion as the antibacterial agent were incorporated into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity as measured by the shake flask method were 7×10-10 C/cm2 and 67% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
A melt-blown nonwoven fabric having a weight per unit area of 10 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.1% by weight of poly[{(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}(2,2,6,6-tetramethyl-4-piperidyl)-imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}] (a hindered amine compound) as the electret stabilizer and 1% by weight of zirconium phosphate carrying a silver ion as the antibacterial agent were incorporated into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity as measured by the shake flask method were 4×10-10 C/cm2 and 69% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.2% by weight of 3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate (a metallic hindered phenol compound) as the electret stabilizer and 0.9% by weight of a zeolite carrying a silver ion as the antibacterial agent were incorporated into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity as measured by the shake flask method were 6×10-10 C/cm2 and 76% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
A melt-blown nonwoven fabric having a weight per unit area of 100 g/m2 was produced from a polypropylene having a volume resistivity of 10×1016 Ω·cm. In the production of the nonwoven fabric, 0.2% by weight of pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (a phenol compound) as the antibacterial agent and 1% by weight of zirconium phosphate carrying a silver ion as the antibacterial agent were incorporated into the polypropylene. A voltage of 30 kV was applied to the nonwoven fabric for 1 min to impart an electret property thereto. The surface charge density and antibacterial activity as measured by the shake flask method were 4×10-10 C/cm2 and 70% in terms of the percentage reduction, respectively. That is, the electret nonwoven fabric was satisfactory in both the properties.
In the electret material of the present invention, the metal ion contained, in the antibacterial agent inhibits the growth of bacteria and microbial cells to exhibit an antibacterial effect and, at the same time, the electret stabilizer traps electric charges to exhibit an electret effect. In other words, the electret material of the present invention has a combination of an antibacterial activity with an electret property. Further, these charges remain stable even when environmental conditions, humidity and temperature vary, which renders the electret material of the present invention useable in making filters, packaging materials, agricultural materials, wipers, various covering materials, head-gear, medical materials, masks, and so forth.
Claims (12)
1. An antibacterial electret material comprising a synthetic organic polymer having a volume resistivity of 1013 Ω·cm or above mixed with 0.01 to 2% by weight of at least one electret stabilizer selected from the group consisting of a hindered amine compound, a nitrogenous hindered phenol compound, a metallic salt hindered phenol compound, a phenol compound, a sulfur compound and a phosphorus compound and 0.1 to 4% by weight of an antibacterial metal-ion-containing inorganic compound selected from the group consisting of a metal-ion-containing zeolite; a metal-ion-containing soluble glass and a metal-ion-containing zirconium phosphate,
whereby antibacterial activity is increased as a result of the presence of said antibacterial metal-ion-containing compound, in comparison to an otherwise similar material which contains no antibacterial metal-ion-containing compound,
said antibacterial electret material having a surface charge density of 1×10-10 C/cm2 or above.
2. An antibacterial electret material according to claim 1, wherein said synthetic organic polymer is an olefin polymer having a volume resistivity of 1015 Ω·cm or above.
3. An antibacterial electret material according to claim 1, wherein said electret stabilizer comprises at least two compounds selected from the group consisting of a hindered amine compound, a nitrogenous hindered phenol compound, a metallic salt hindered phenol compound, a phenol compound, a sulfur compound and a phosphorus compound and the total content thereof is 0.01 to 0.2% by weight.
4. An antibacterial electret material according to claim 1, wherein said metal-ion-containing inorganic compound comprises a zeolite containing a silver ion.
5. An antibacterial electret material according to claim 1, wherein said metal-ion-containing inorganic compound contains a metal ion selected from the group consisting of silver, copper, zinc, mercury, tin, lead, bismuth, chromium and thallium ions.
6. An antibacterial electret material according to claim 1, wherein said metal-ion-containing inorganic compound comprises a soluble glass containing a silver ion.
7. An antibacterial electret material according to claim 1, whereon said metal-ion-containing inorganic compound comprises a zeolite containing a silver ion and a soluble glass containing a silver ion.
8. An antibacterial electret material according to claim 1, wherein said metal-ion-containing inorganic compound comprises zirconium phosphate containing a silver ion.
9. An antibacterial electret material according to claim 1, which is in the form of a fiber.
10. An antibacterial electret material according to claim 1, which is in the form of a nonwoven fabric.
11. An antibacterial electret material according to claim 1, which is in the form of a film.
12. An antibacterial electret material according to claim 1, which is in the form of paper.
Applications Claiming Priority (3)
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JP00172292A JP3286998B2 (en) | 1992-01-08 | 1992-01-08 | Antibacterial electret material |
JP4-001722 | 1992-01-08 | ||
PCT/JP1993/000016 WO1993014510A1 (en) | 1992-01-08 | 1993-01-08 | Antibacterial electret material |
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US08/108,644 Expired - Fee Related US5556618A (en) | 1992-01-08 | 1993-01-08 | Antibacterial electret material |
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EP (1) | EP0575629B1 (en) |
JP (1) | JP3286998B2 (en) |
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CA (1) | CA2105651C (en) |
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- 1993-01-08 EP EP93901567A patent/EP0575629B1/en not_active Expired - Lifetime
- 1993-01-08 KR KR1019930702524A patent/KR100191345B1/en not_active IP Right Cessation
- 1993-01-08 CA CA002105651A patent/CA2105651C/en not_active Expired - Fee Related
- 1993-01-08 WO PCT/JP1993/000016 patent/WO1993014510A1/en active IP Right Grant
- 1993-01-08 DE DE69311977T patent/DE69311977T2/en not_active Expired - Fee Related
- 1993-01-08 US US08/108,644 patent/US5556618A/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
DE69311977D1 (en) | 1997-08-14 |
EP0575629A4 (en) | 1994-04-06 |
EP0575629A1 (en) | 1993-12-29 |
CA2105651C (en) | 1998-04-07 |
JPH05190389A (en) | 1993-07-30 |
JP3286998B2 (en) | 2002-05-27 |
TW228007B (en) | 1994-08-11 |
DE69311977T2 (en) | 1997-11-06 |
EP0575629B1 (en) | 1997-07-09 |
KR100191345B1 (en) | 1999-06-15 |
WO1993014510A1 (en) | 1993-07-22 |
CA2105651A1 (en) | 1993-07-09 |
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